Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
  • C07F9/165—Esters of thiophosphoric acids
  • C07F9/20—Esters of thiophosphoric acids containing P-halide groups

Definitions

• the present invention relates to an unobvious process for the production of certain phosphorochloridothiolates which can be used as the starting materials for certain organic phosphate esters that are useful as agricultural chemicals.
• R 2 represents alkyl
• R 3 represents alkyl
• reaction (iii) 0.5 mole of phosphorus trichloride is used per mole of the trialkyl phosphite, and in the reaction (iv) 2 moles of the alcohol and 2 moles of a dehydrochlorinating agent are reacted with 1 mole of phosphorus trichloride.
• trialkyl phosphite and the alkyl dichlorophosphite are always present as impurities, the separation of the desired dialkyl chlorophosphite is difficult even by distillation, because it is unstable and it has a similar vapor pressure similar to those of the other components and azeotropic properties; a great reduction in yield occurs as a result.
• the trialkyl phosphite rapidly reacts with a sulphenyl chloride in the subsequent reaction shown as follows:
• the present invention now provides a process for producing a phosphorochloridothiolate of the general formula: ##STR10## wherein R 1 represents alkyl, alkoxyalkyl or aryl that is optionally substituted by alkyl, alkoxy or halogen, and
• R 2 represents alkyl
• R 2 is as defined above
• R 2 is as defined above
• R 2 is as defined above
• R 1 is as defined above,
• R 2 is as defined above
• R 2 is as defined above
• R 2 is as defined above
• R 2 is as defined above
• R 1 is as defined above,
• R 2 is as defined above
• a mixture of the alkyl dichlorophosphite and the dialkyl chlorophosphite with an extremely low content of the trialkyl phosphite can be obtained either by reacting the trialkyl phosphite of the formula (I) with about 0.6-1.5 times the molar amount of phosphorus trichloride and at a temperature from about -30° to 100° C., or by reacting phosphorus trichloride with about 1.2-1.8 times the molar amount of an alcohol of the formula (VII) in the presence of a dehydrochlorinating agent (the dehydrochlorinating agent preferably being a base present in molar amount equal to that of the alcohol) and at a temperature from about -30° to 100° C.
• a dehydrochlorinating agent the dehydrochlorinating agent preferably being a base present in molar amount equal to that of the alcohol
• the phosphorochloridothiolate and phosphoro dichloridothiolate thus obtained can be quantitatively analyzed by gas chromatography, so that the phosphorodichloridothiolate thus determined without any separation can be reacted with, preferably, the equimolar amount of the alcohol of the formula (VII) and preferably the equimolar amount of the dehydrochlorinating agent in the presence of an appropriate solvent, at a temperature from about -20° to 50° C., selectively to esterify the phosphorodichloridothiolate to the final product, the phosphorochloridothiolate. Under these optimum reaction conditions, substantially no formation of the phosphorothiolate due to the reaction of the phosphoro chloridothiolate and the alcohol was observed, although such a reaction could well have been expected.
• R 1 represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert.-butyl, n- or iso-amyl, n-hexyl, methoxyethyl, ethoxymethyl, n- or isopropoxymethyl, n-, iso-, sec- or tert-butoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n- or iso-propoxyethyl, 2-n-, iso-, sec- or tert-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl or phenyl or naphthyl, either of which may optionally carry one or more substituents selected from methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or iso-amyl,
• R 2 represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n- or iso-amyl or n-hexyl.
• trialkyl phosphites of the formula (I) trimethyl phosphite, triethyl phosphite, tri-n- (or iso-) propyl phosphite and tri-n- (iso-, sec- or tert-) butyl phosphite.
• Examples of the sulphenyl chlorides of the formula (IV) are: methyl-, ethyl-, n- (or iso-) propyl, n- (iso-, sec- or tert-)-butyl, n- or iso-amyl, and n-hexyl-sulphenyl chlorides; methoxymethyl-, ethoxymethyl-, n- (or iso-) propoxymethyl-, n- (iso-, sec- or tert-) butoxymethyl-,2-methoxyethyl-, 2-ethoxyethyl-, 2-n- (and iso-) propoxyethyl-, 2-n- (iso-, sec- or tert-) butoxyethyl, 3-methoxypropyl- and 3-ethoxypropyl-sulphenyl chlorides; 2- (3- or 4-) methyl-, [ethyl-, or n- (or iso-) propy
• a solvent or a diluent may be employed if desired.
• any inert solvent or diluent can be used.
• solvents and diluents are aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethylene and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran: ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl is
• the process of the present invention is preferably carried out in the presence of an acid-binding agent, i.e. the dehydrochlorinating agent.
• acid binders are the customary alcoholates and tertiary amines, such as triethylamine, dimethylbenzylamine, diethylaniline or pyridine.
• the S-n-propyl phosphorodichloridothiolate contained in the mixture was reacted with stoichiometric amounts of ethanol and triethylamine to obtain 87 g of O-ethyl-S-n-propyl phosphorochloridothiolate.
• the purity was 95.5%. Therefore, the yield based on the total phosphorus in the raw materials was 82%.
• the S-n-propyl phosphorodichloridothiolate contained in the mixture was reacted with stoichiometric amounts of ethanol and triethylamine to obtain 75 g of O-ethyl-S-n-propyl phosphorochloridothiolate.
• the purity was 91.1%. Therefore, the yield based on the total phosphorus in the raw materials was 84%.

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• 1979
  • 1979-04-19 JP JP4719279A patent/JPS55139394A/ja active Granted
• 1980
  • 1980-03-19 US US06/131,714 patent/US4290978A/en not_active Expired - Lifetime
  • 1980-04-05 DE DE8080101841T patent/DE3063652D1/de not_active Expired
  • 1980-04-05 EP EP80101841A patent/EP0019700B1/de not_active Expired
  • 1980-04-16 CS CS802657A patent/CS210631B2/cs unknown
  • 1980-04-16 DD DD80220499A patent/DD151450A5/de unknown
  • 1980-04-16 HU HU80927A patent/HU185012B/hu unknown
  • 1980-04-16 BR BR8002353A patent/BR8002353A/pt unknown
  • 1980-04-16 IL IL59844A patent/IL59844A/xx unknown
  • 1980-04-17 PL PL1980223542A patent/PL126263B1/pl unknown
  • 1980-04-18 DK DK165980A patent/DK149472C/da not_active IP Right Cessation

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